CN1306538A - Organometallic complexes comprising cationic heterocyclic carbenes - Google Patents

Organometallic complexes comprising cationic heterocyclic carbenes Download PDF

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CN1306538A
CN1306538A CN99807665A CN99807665A CN1306538A CN 1306538 A CN1306538 A CN 1306538A CN 99807665 A CN99807665 A CN 99807665A CN 99807665 A CN99807665 A CN 99807665A CN 1306538 A CN1306538 A CN 1306538A
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organometallic complex
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CN1152037C (en
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G·伯特兰德
L·斯戴尔奇格
O·古尔莱特
C·布隆
H·格尼茨卡
P·布拉丁
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Rhone Poulenc Fibres SA
Rhodia Fiber and Resin Intermediates SAS
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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    • C07—ORGANIC CHEMISTRY
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    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0073—Rhodium compounds
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    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages

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Abstract

The invention relates to novel organometallic complexes comprising cationic heterocyclic carbenes. It also relates to a method for preparing said complexes from dicationic heterocyclic precursor compounds. It further relates to the use as catalysts of said organometallic complexes for a certain number of chemical reactions.

Description

The organometallic complex that comprises cationic heterocyclic carbenes
The present invention relates to comprise the novel organometallic complex of cationic heterocyclic carbenes.
The present invention also relates to dication heterocyclic precursor compound as the approach of this type of organometallic complex of preparation.
The invention still further relates to the preparation method of above-mentioned organometallic complex.
At last, the present invention also relates to described organometallic complex purposes as catalyzer in some chemical reactions.
The organometallic complex that comprises heterocycle carbine was disclosed in the prior art.Patent EP-A-0,721,953 disclose and have comprised the non-cationic heterocycle carbine that is derived from tetrahydroglyoxaline or pyrazoline and the title complex of the periodic table of elements the 8th, 9 and 10 family's metals.Patent EP-A-0,798,041 disclose comprise be derived from have 5-, 6-or 7-unit ring and comprise non-cationic heterocycle carbine and a kind of title complex that is selected from the metal of palladium, rhodium, nickel, ruthenium and cobalt of all cpds of one or more nitrogen and/or sulphur atom.
This type of title complex is very stable compound, also has the advantage that is not formed with toxic byproduct simultaneously in decomposition course.Yet their shortcoming is to be used for the peracidity medium, and oxidation state is that 0 metal complexes is water insoluble, and this has limited their Application Areas.
Thereby the present invention at first relates to the organometallic complex that comprises heterocycle carbine, it is characterized in that they are corresponding to logical formula I:
[(Z +X -) mML n] Y (I) wherein:
-Z +Expression 1,2,4-triazole-5-subunit ion, wherein at least a portion annular atoms is contained the hydrocarbyl group replacement,
-L represents ligand, and it can be ion or neutral,
-M represent to be selected from The Chemical Rubber company " chemistry and physics handbook, the 51st edition " (1970-1971) in the metal of 1b, 2b, 3b, 4b, 5b, 6b, 7b and 8 family's transition element in the disclosed periodic table of elements,
-X-represents the organic or inorganic negatively charged ion,
-m represents 1～6 integer,
-n represents 0～5 integer,
-m and n sum are equal to or less than 6,
-Y represents to make metal complexes to be electroneutral negatively charged ion or positively charged ion.
For simplicity, the compound that also comprises the formula I of anti-electron ion Y is called as organometallic complex or metal complexes in this application.
1,2,4-triazole-5-subunit ion Z +Corresponding to logical formula II: R wherein 1, R 2, R 3And R 4Can represent identical or differently:
-straight or branched alkyl or cycloalkyl,
-aryl,
-comprise one or more substituent alkyl, described substituting group for example be aryl, alkoxyl group, halogen atom or hydrophilic radical as:
-COOM 1,-SO 3M 1Or-PO 3M 1, M 1Expression is selected from the inorganic of proton or organic cation residue, be derived from the positively charged ion of basic metal or alkaline-earth metal or wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～4 carbon atom 4,
-N (R) 3Y a, symbol R can represent hydrogen atom identical or differently or have the alkyl of 1～12 carbon atom, Y in the formula aRepresent inorganic or organic anion,
-OH，
-aryl or aralkyl or on ring, comprise one or more substituent cycloalkyl, described substituting group for example be alkyl, alkoxyl group, halogen atom or hydrophilic radical as:
-COOM 1,-SO 3M 1Or-PO 3M 1, M 1Expression is selected from the inorganic of proton or organic cation residue, be derived from the positively charged ion of basic metal or alkaline-earth metal or wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～12 carbon atom 4,
-N (R) 3Y a, symbol R can represent hydrogen atom identical or differently or have the alkyl of 1～12 carbon atom in the formula, Ya represents inorganic or organic anion,
-OH，
R 3Also represent hydrogen atom,
R 1And/or R 4Also can represent separately by alkylidene group or arylidene and 1,2, the organic ligand residue of 4-triazole-5-subunit ionic nitrogen atom bonding, this ligand residue might be phosphorous acid ester residue, phosphinate residue, phosphinate residue, phosphine residue or aliphatic series, alicyclic, aromatics or heterocycle tertiary amine residue and as with the ligand L of metal M.
Above-mentioned organic ligand residue can for example be derived from phenyl-phosphite that replaced by substituting group defined above or unsubstituted or alkyl ester, or by phospho acid phenyl ester that substituting group defined above replaced or unsubstituted or alkyl ester, or by phosphonous acid phenyl ester that substituting group defined above replaced or unsubstituted or alkyl ester, or by phosphniline that substituting group defined above replaced or unsubstituted or alkylphosphines.
In this case, by R as defined above 1And/or R 41,2 of group replacement, 4-triazole-5-subunit ion is bidentate or tridentate ligand.
L represents ionic ligand for example halogenide or prussiate, or neutral ligand for example carbon monoxide, isonitrile, phosphine, organophosphite, phosphonic acid ester or phosphinate.
M preferably represents to be selected from the metal of nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium or mercury.
These metals can be their various oxidation state, comprise the O oxidation state.
The X-negatively charged ion is the organic or inorganic negatively charged ion, and for example halogenide still is preferably selected from according to the defined weakly coordinating anion of the metal M of being considered.They mainly constitute 1,2, the 4-triazole-anti-electron ion of 5-subunit ionic.
As the non-limitative example of this type of weakly coordinating anion, can mention trifluoromethayl sulfonic acid root, tetrafluoroborate, hexafluoro-phosphate radical, aluminum tetrachloride, tetrabormated aluminium, tetrafluoride aluminium, tetraiodide aluminium, four gallium chlorides, tetrabormated gallium, tetrafluoride gallium or tetraiodide gallium.
The invention still further relates to dication heterogeneous ring compound purposes as precursor in the preparation of the organometallic complex of logical formula I.These dication heterogeneous ring compounds are corresponding to logical formula III:
Figure A9980766500081
Wherein
-symbol R 1, R 2, R 3And R 4Regard to 1,2 of formula II on having, the implication shown in 4-triazole-5-subunit ion,
-X-represents a kind of negatively charged ion, for example for shown in the logical formula I those.
The dication heterogeneous ring compound of logical formula III can be by making wherein X and R 2The formula XR of implication shown in above having 2Compound with have a R 1, R 3And R 4Substituent triazole derivative reacts and prepares.Described preparation method also can divide several steps to carry out, and each step is to make triazole derivative to be incorporated into substituting group and formula XR in the used triazole formula according to needs 1Or XR 3Or XR 4Compound reaction so that obtain the dication heterogeneous ring compound of formula III.Reaction conditions can be according to the article of T.J.Curphey and K.S.Prasad, Journal of Org.Chem., and 1972,37,2259 described working method are made amendment.
The organometallic complex of formula I can prepare by dication heterogeneous ring compound and the compounds of metal M reaction that makes logical formula III in the presence of inorganic or organic bases.This alkali can be the association negatively charged ion of compounds of metal M or can be joined in the reaction mixture independently.This reaction generally can be by adding compounds of metal M and adding inorganic if desired or organic bases carries out in liquid medium in the solution of compound (III) or suspension.Obviously, the adding order of various reactants can change.The reaction at room temperature or preference as under 25～150 ℃ temperature, carrying out.This temperature usually is in the reflux temperature that wherein carries out synthetic liquid.The separation of the title complex of formula I can be carried out according to chemical common method, for example by filtration, centrifugal or extraction.The dication heterogeneous ring compound of the title complex of formula I and formula III is generally characterized by nucleus magnetic resonance (NMR) or infrared or X-ray diffraction.
The organometallic complex of formula I can be used as the catalyzer of many chemical reactions.
The dication heterogeneous ring compound of the organometallic complex of most of formula I and formula III presents weak solvability or presents insoluble in most of nonpolar or weakly polar organic solvent such as paraffinic hydrocarbons, naphthenic hydrocarbon, halogenated paraffin, aromatic hydrocarbons, alkylaromatic hydrocarbon or ethers.In contrast, they dissolve in the polar solvent.Therefore, dicationic compounds which dissolves in tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) (DMSO), nitrile (for example acetonitrile) or the water especially.Therefore organometallic complex of the present invention dissolves in nitrile (for example acetonitrile), DMSO or the water especially.These performances make these all cpds more easily separate, and particularly pass through liquid/liquid extraction.In addition, this makes and might carry out catalysis in two-phase medium.
Non-limitative example as this type of reaction; can mention the particularly hydrosilylation effect of alkene or alkynes in the presence of ruthenium complexe; the hydrosilylation effect of ketone in the presence of ruthenium or rhodium complex; Heck reaction in the presence of palladium complex; at ruthenium; rhodium; there are alkene down in platinum or palladium complex; aldehyde; acid; the hydrogenization of alkene acid amides and nitroaromatic; the hydroformylation of alkene and hydroformylation effect in the presence of rhodium complex; the hydrocyanation of alkene in the presence of nickel complex; furans is synthetic in the presence of ruthenium complexe; the metathesis of alkene in the presence of ruthenium complexe, or in the presence of nickel complex the polyreaction of acrylate.
Synthetic EXAMPLE Example 1 compound of the precursor of formula III (a) synthetic of III:
Figure A9980766500091
According to J.Org.Chem., 1972,37, p.2259 described working method is stirring and 1, refluxes in the 2-ethylene dichloride down with the trifluoromethanesulfonic acid methyl esters to 1H-1,2,4-methyl-triazole carry out methylating for twice (2 and 4 of ring).
The brown precipitate thing that forms is filtered, and with 1, the washing of 2-ethylene dichloride is till obtaining white powder.(III fusing point a) is 160-162 ℃ to this solid.
It is characterized in that:
-RMN 1H(DMSO-d 6):δ4.22(s,3H,CH 3N),4.50(s,6H,CH 3N),10.79(s,2H,
Hcycl).
-RMN 13C(H)(CD 3CN):δ38.67(s,CH 3N),38.87(s,2CH 3N),120.35(q, 1J CF=
320.1Hz, CF 3), 147.72 (s, 2C Cycl). synthesizing of embodiment 2 compounds (III b):
Figure A9980766500101
Should synthetic carry out in two steps.At first, by to the trifluoromethanesulfonic acid isopropyl ester 1, stoichiometry adds 1H-1 in the solution in the 2-ethylene dichloride, 2,4-methyl-triazole (under agitation refluxing 3 hours) is combined in 4 with sec.-propyl and goes up (R 4Group).The productive rate that obtains the yellow oil form is 91% following formula: compound:
Figure A9980766500102
2.5ml trifluoromethanesulfonic acid methyl esters (22mmol) is added this compound of 5g (18mmol) at 20ml 1, in the solution of 2-ethylene dichloride, mixture was under agitation refluxed 24 hours.Form the brown precipitate thing, this throw out is filtered, use 1 then, the washing of 2-ethylene dichloride is till obtaining white powder.
The fusing point of this solid (III b) is 163-165 ℃, is 73% with respect to the productive rate of the midbody compound that is added.
It is characterized in that :-RMN 1H (CD 3CN): δ 1.65 (d, 3JHH=6.58Hz, 6H, CH 3CH), 4.34 (s, 3H, CH 3N), 5.03 (sept, 3JHH=6.58Hz, 1H, [CH 3] 2CHN), 10.22 (s, 2H, H Cycl) .-RMN 13C (CD 3CN): δ 21.51 (s, CH 3CH), 38.71 (s, CH 3N), 58.88 (s, [CH 3] 2CHN), 120.35 (q, 1J CF=320,1Hz, CF 3); 145.22 (s, 2C Cycl). synthesizing of embodiment 3 compounds (III c):
Figure A9980766500111
Should synthetic carry out in two steps.At first, according to J.Prakt.Chem., 1988,330,3,325 described working method prepare the compound of following formula:
This compound of reflux 4 days in the trifluoromethanesulfonic acid methyl esters under agitation.Form the brown precipitate thing, this throw out is filtered, use 1 then, the washing of 2-ethylene dichloride is till obtaining white powder.With respect to the compound that adds in second step, obtain this solid (III c) with productive rate 50%.
It is characterized in that :-RMN 1H (CD 3CN): δ 4,22 (S, 3H, CH 3N), 7,4-8,4 (not offering an explanation the peak, the H phenyl), 10,34 (s, 1HH Ring). synthesizing of embodiment 4 compounds (III d):
Figure A9980766500114
Should synthetic carry out in two steps.At first, according to J.Prakt.Chem., 1988,330,3,325 described working method prepare the compound of following formula:
Figure A9980766500121
Under agitation 1, in the 2-ethylene dichloride with 3 these compounds of equivalent trifluoromethanesulfonic acid methyl esters reflux 2 days.Form the brown precipitate thing, this throw out is filtered, use 1 then, the washing of 2-ethylene dichloride is till obtaining white powder.With respect to the compound that adds in second step, obtain this solid (III d) with productive rate 69%, its fusing point is 190.5-191.3 ℃.
It is characterized in that :-RMN 1H (CD 3CN): δ 3.04 (s, 3H, CH 3), 4.19 (s, 3H, CH 3N), 7.8-8.1 (not differentiating the peak, 10H, 1 phenyl H), 10.51 (s, 1H, H Ring) .-RMN 13C (CD 3CN): δ 12.31 (s, CH 3C), 38.04 (s, CH 3N), 126.70 (s, 2CH phenyl), 128.02 (s, C phenyl), 128.49 (s, 2CH phenyl), (130.07 s, C phenyl), 131.56 (s, 2CH phenyl), 131.83 (s, 2CH phenyl), (134.04 s, 1CH phenyl), 135.88 (s, 1CH phenyl), 120.35 (q 1J CF=320.1Hz, CF 3), 145.58 (s, CH Ring), 157.66 (s, C RingCH 3).
Proton coupling spectrum shows the coupling constant of CH in the triazole ring 1J CH=240Hz.Synthesizing of embodiment 5 compounds (III e):
Figure A9980766500122
Should synthetic carry out in two steps.At first, according to J.Prakt.Chem., 1988,330,3,325 described working method prepare following formula: compound:
Figure A9980766500131
Under agitation 1, in the 2-ethylene dichloride with 3 these compounds of equivalent trifluoromethanesulfonic acid methyl esters reflux 2 days.Form the brown precipitate thing, this throw out is filtered, use 1 then, the washing of 2-ethylene dichloride is till obtaining white powder.With respect to the compound that adds in second step, obtain this solid (III e) with productive rate 71%, its fusing point is 180.0 ℃.
It is characterized in that :-RMN 1H (CD 3CN): δ 4.08 (s, 3H, CH 3N), 4.20 (s, 3H CH 3N), 4.46 (s, 3H, CH 3N), 7.8-8.1 (not differentiating the peak, 10H, 5H phenyl), 10.16 (s, 1H, H Ring) .-RMN 13C (CD 3CN): δ 37.88 (s, CH 3N), 38.36 (s, CH 3N), 39.42 (s, CH 3N), 130.78 (s, C phenyl), 131.97 (s, 2CH phenyl), 132.15 (s, 2CH phenyl), 137.35 (s, CH phenyl), 131.83 (s, 2CH phenyl), 120.35 (q, 1J CF=320.1Hz, CF 3), 147.35 (s, CH Ring), 156.48 (s, C Ring). synthesizing of embodiment 6 compounds (III f): this compound of heat 2 days.Form the brown precipitate thing, this throw out is filtered, use 1 then, the washing of 2-ethylene dichloride is till obtaining white powder.With respect to the compound that adds in second step, obtain this solid (III f) with productive rate 95%, its fusing point is 194.4 ℃.-RMN 1H (acetone d 6): δ 3.35 (s, 3H, CH 3C), 4.46 (s, 3H, CH 3N), 4.69 (s, 3H, CH 3N), 4.77 (s, 3H, CH 3N), 10.77 (s, 1H, H Ring) .-RMN 13C (acetone d 6) δ 10.53 (s, CH 3C), 35.91 (s, CH 3N), 36.26 (s, CH 3N), 37.99 (s, CH 3N), 120.35 (q, 1J CF=320.1Hz, CF 3), 145.35 (s, CH Ring), 157.31 (s, C RingCH 3). synthetic EXAMPLE Example 7Ag (I) compound of the organometallic complex of formula I (a) synthetic of I:
Figure A9980766500141
0.4g (2.4mmol) silver acetate is joined among the embodiment 1 the 1g dicationic compounds which of preparation, and (III is a) in the suspension in 20ml tetrahydrofuran (THF) (THF).Under refluxing, stirred this mixture 2 hours.Form and the immiscible brown oil of THF, several times with 10ml THF washing.Behind the evaporating solvent, obtain the photosensitivity brown solid (with respect to dicationic compounds which (III productive rate a) is 82%).
This title complex has following eigenwert :-RMN 1H (CD 3CN): δ 4.01 (s, 3H, NCH 3), 4.19 (s, 3H, CH 3N-NCH 3), 4.22 (s, 3H, CH 3N-NCH 3), 9.72 (s, 1H, CH) .-RMN 13C (CD 3CN): δ 37.2 (NCH 3), 38.5 (NCH 3), 38.6 (NCH 3), 121.1 (q, 1J CF=320.1Hz, CF 3), 144.8 (CH); 189.2 (CAg). synthesizing of embodiment 8 Hg (II) compounds (I b):
Figure A9980766500142
0.16g oxalic acid mercury (being dried 12 hours under 50 ℃ of vacuum in advance) and 1ml dimethyl sulfoxide (DMSO) (DMSO) are joined in the suspension of 0.43g dicationic compounds which (III e) in 20ml tetrahydrofuran (THF) (THF) of preparation among the embodiment 5.At room temperature stirred this mixture 24 hours.Form the brown precipitate thing that only dissolves in the high polar solvent.This solid washs several times so that remove trace acetate with THF.By ether slowly diffusion in the methanol solution of this title complex, with thus obtained title complex recrystallization.The fusing point of the title complex of recrystallization (I b) is 85.4-87 ℃.(III e) obtains productive rate 86% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (CD 3OD): δ 4.70 (s, 12H, NC H 3, 4J H-Hg=12.8), 4.29 (s, 6H, CH 3N, 4J H-Hg=8,5Hz), 7.9-8.2 (not differentiating the peak, 10H, H phenyl)-RMN 13C (CD 3OD): δ 38.79 (CH 3N-NCH 3), 41.75 (NCH 3), 121.1 (q, 1J CF=320.1Hz, CF 3), 156.88 (C-Ph, ( 3J+ 2J) C-Hg=86Hz), 183.78 (CHg, J1 CHg=3275Hz).
Its structure is also determined by X-ray diffraction.Synthesizing of embodiment 9 Ni (II) compounds (I c):
Figure A9980766500151
The 2.4g dicationic compounds which (III e) of preparation among the embodiment 5 is added in 0.442g oxalic acid nickel and the suspension of 0.75g sodium iodide in 50ml THF.Under refluxing, stirred this mixture 2 hours.Form painted throw out, this throw out is filtered and wash several times with THF.-30 ℃ in the acetone mixture with thus obtained title complex recrystallization.The title complex of recrystallization (I c) is red, and its fusing point is 310.7 ℃ and (decomposes: the crystal blackening).(III e) obtains productive rate 85% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (acetone-d 6): δ 7.8-8.0 (wide, 10H, H phenyl), 4.88-4.84 (2s, 6H, NCH 3), 4.54-4.49 (2s, 6H, CH 3N), 4.42-4.41 (2s, 6H, CH 3N) .-RMN 13C (CD 3OD): δ 37.0 (CH 3N), 37.9 (CH 3N), 38.4 (CH 3N), 121.1 (q, 1J CF=320,1Hz, CF 3), 130.5-130.8-134.8 (C phenyl), 153.4 (C-Ph), 188.2 (C-Ni).
Its structure is also determined by X-ray diffraction.Synthesizing of embodiment 10 Ni (II) compounds (I d):
The 0.425g dicationic compounds which (III f) of preparation among the embodiment 6 is added in 0.090g oxalic acid nickel and the suspension of 0.15g sodium iodide in 25ml THF.Under refluxing, stirred this mixture 2 hours.Form painted throw out, this throw out is filtered and wash several times with THF.-30 ℃ in the acetone mixture with thus obtained title complex recrystallization.The title complex of recrystallization (I d) is red, and its fusing point is 300-305 ℃ and (decomposes: the crystal blackening).(III f) obtains productive rate 79% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (acetone-d 6): δ 4.88-4.84 (2s, 6H, NCH 3), 4.54-4.49 (2s, 6H, CH 3N), 4.42-4.41 (2s, 6H, CH 3N), 2.63 (s, 6H, C-CH 3) .-RMN 13C (CD 3OD): δ 13.86 (C-C H 3), 36.1 (CH 3N), 37.6 (CH 3N), 38.5 (CH 3N), 121.1 (q, 1J CF=320,1Hz, CF 3), 154.8 (C-Me), 187.6 (C-Ni).
Its structure is also determined by X-ray diffraction.Synthesizing of embodiment 11 Ni (II) compounds (I e):
Figure A9980766500162
With among the embodiment 1 preparation the 0.935g dicationic compounds which (III a) adds in 0.200g oxalic acid nickel and the suspension of 0.34g sodium iodide in 30ml THF.Under refluxing, stirred this mixture 2 hours.Form painted throw out, this throw out is filtered and wash several times with THF.By ether slowly diffusion in the acetonitrile solution of this title complex, with thus obtained title complex recrystallization.In the acetone mixture, carry out recrystallization at-30 ℃.The title complex of recrystallization (I e) is red.(III a) obtains productive rate 70% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (acetone-d 6): δ 4.38-4.35 (2s, 6H, CH 3N), 4.68-4.65 (2s, 6H, CH 3N), 4.99-4.96 (2s, 6H, NCH 3), 9.32 (s, 2H, CH). synthesizing of embodiment 12 Pd (II) compounds (I f):
Figure A9980766500171
The 0.472g dicationic compounds which (III e) of preparation among the embodiment 5 is added in 0.112g palladium diacetate and the suspension of 0.30g sodium iodide in 60ml THF.Under refluxing, stirred this mixture 2 hours.Form painted throw out, this throw out is filtered and wash several times with ether.At-30 ℃ of title complex recrystallizations that in the acetone mixture, will obtain thus.It is the yellow crystals form.The fusing point of the title complex of recrystallization (I f) is 211-213 ℃ (decompose: crystal becomes brown).In reaction process, all trifluoromethanesulfonic acid root negatively charged ion are all replaced by the iodine negatively charged ion.(III e) obtains productive rate 51% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (DMSO-d 6): δ 7.8-8.1 (wide, 10H, H phenyl), 4.49-4.53 (2s, 6H, NCH 3), 4.21 (s, 6H, CH 3N), 4.10-4.13 (2s, 6H, CH 3N) .-RMN 13C (DMSO-d 6): δ 37.2 (CH 3N), 38.3 (CH 3N), 39.9 (CH 3N), 130.1-130.9-134.5 (C phenyl), 152.4 (C-Ph), 174.5 (C-Pd).
Its structure is also determined by X-ray diffraction.Synthesizing of embodiment 13 Pd (II) compounds (I g):
Figure A9980766500172
The 0.425g dicationic compounds which (III f) of preparation among the embodiment 6 is added in 0.112g palladium diacetate and the suspension of 0.30g sodium iodide in 60ml THF.Under refluxing, stirred this mixture 2 hours.Form painted throw out, this throw out is filtered and wash several times with ether.At-30 ℃ of title complex recrystallizations that in the acetone mixture, will obtain thus.Its crystalline form that takes on a red color.The fusing point of the title complex of recrystallization (I g) is 206-212 ℃ (decompose: crystal becomes brown).In reaction process, all trifluoromethanesulfonic acid root negatively charged ion are all replaced by the iodine negatively charged ion.(III f) obtains productive rate 60% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (DMSO-d 6): δ 4.41-4.40 (2s, 6H, NCH 3), 4.29 (s, 6H, CH 3N), 4.16-4.15 (2s, 6H, CH 3N), 2.95 (6H, C-CH 3). synthesizing of embodiment 14 Ni (0) compounds (I h):
Figure A9980766500181
Synthetic method A
Dilution 1ml nickel tetracarbonyl in the acetonitrile of and the degassing anhydrous at 40ml.380 μ l pyridines and 660 μ l triethylamines are added in the resultant solution.Use dropping funnel to drip solution in the acetonitrile of the 2.0g dicationic compounds which (III f) of preparation among the embodiment 6 and degassing anhydrous at 60ml.Observe gas and discharge the solution becomes yellowly.When adding all solution, continue to stir other 1 hour.Make the volume of reaction soln reduce 2/3rds by the vaporising under vacuum solvent, add the ether of the 200ml degassing then.Form the throw out of title complex (I h), this throw out is filtered and wash several times with ether.At-30 ℃ of title complex recrystallizations that in the acetone mixture, will obtain thus.It is the yellow crystals form.Can't accurately measure its fusing point (decompose: crystal becomes brown).(III f) obtains productive rate 26% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (DMSO-d 6): δ 4.00 (s, 6H, NCH 3), 3.99 (s, 6H, CH 3N), 3.78 (s, 6H, CH 3N), 2.72 (6H, C-CH 3).
Observe at 1982cm by infrared spectra -1And 1906cm -1The bands of a spectrum (CO) at place.
Its structure is also determined by X-ray diffraction.
Find by ultimate analysis:
-28.99%C (theoretical value 28.89%)
-3.36%H (theoretical value 3.63%)
-12.39%N (theoretical value 12.62%).
Synthetic method B
150mg activated metal Zn powder (10 equivalent) is added in the solution in the acetonitrile of the 0.2g organometallic complex (I d) of preparation among the embodiment 10 and degassing anhydrous at 10ml.Solution is positioned under the carbon monoxide atmosphere.When stirring beginning, react.The solution flavescence.Use the valve tube filtering solution, with the mode described in the method A it is handled (adding ether so that the precipitation organometallic complex) then.With respect to the organometallic complex (I d) that adds, the productive rate that obtains is 48%.Carry out with method A in identical analysis and sign, and come to the same thing.Synthesizing of embodiment 15 Rh (I) compounds (I j):
The solution of 0.277g two (carbonyl) methyl ethyl diketone rhodium in 10ml THF is added in the 0.456g dicationic compounds which (III f) and the suspension of 0.16g NaI in 40ml THF of preparation among the embodiment 6.Stirred the mixture 2 days at 50 ℃.Behind evaporating solvent, reclaim brown solid, and with the ether washing several times.Productive rate with respect to dicationic compounds which (III f) is 70%.
This title complex has following eigenwert :-RMN 1H (DMSO-d 6): δ 4.47 (s, 3H, NCH 3), 4.28 (s, 3H, CH 3N), 4.20 (s, 3H, CH 3N), 2.96 (s, 3H, C-CH 3) .-RMN 13C (DMSO-d 6): δ 10.5 (s, C-CH 3), 35.2 (s, NCH 3), 36.8 (s, CH 3N), 37.9 (s, CH 3N), 154.2 (s, C-CH 3), 183.0 (d, 1J (Rh-C)=82.9Hz, CO), 188.1 (d, 1J (Rh-C)=42.2Hz, the C Cabbeen).
Observe at 1975cm by infrared spectra -1The bands of a spectrum (CO) at place.Synthesizing of embodiment 16 Rb (I) compounds (I k):
Figure A9980766500201
The solution of 0.200g two (carbonyl) methyl ethyl diketone rhodium in 10ml THF is added the 0.16g dicationic compounds which of preparation among the embodiment 1, and (III is a) in the suspension in 10ml THF.Stirred the mixture 15 hours at 50 ℃.Form the brown solid throw out, this throw out with the ether washing several times.(III a), the productive rate of title complex (I k) is 67% with respect to dicationic compounds which.
This title complex has following eigenwert :-RMN 1H (DMSO-d 6): δ 4.20 (s, 3H, NCH 3), 4.22 (s, 3H, CH 3N), 4.25 (s, 3H, CH 3N), 9.66 (s, 1H, CH) .-RMN 13C (DMSO-d 6): δ 38.6 (s, NCH 3), 38.7 (s, NCH 3), 39.1 (s, CH 3N), 37.9 (s, CH 3N), 121.1 (q, 1J CF=320,1Hz, CF 3), 145.5 (s, CH), 186.1 (d, 1J (Rh-C)=76Hz, CO), 187.9 (d, 1J (Rh-C)=43.3Hz, the C Cabbeen).
Observe cm by infrared spectra at 2029 (i) -1With 1985 (m) cm -1The bands of a spectrum (CO) at place.Embodiment 17 is by the styrene catalyzed hydrocarbonylation of Rh (I) compound (I j)
Carry out cinnamic hydrocarbonylation in comprising the 100ml stainless steel reactor of double-jacket, the effect of this chuck is to heat by oil circulation under the thermostat controlled temperature of use.The lid of reactor is equipped with supplies gas under pressure or vent valve, accurately measuring cell, safety valve and can shift the ball valve of solution by syringe.With Teflon Crucible is installed in the autoclave, and this crucible comprises a magnetic bar that is used for reaction stirred.
With Rh (I) title complex (I j) of preparation among the embodiment 15 (40mg) and 100mg triphenyl phosphine (is 5 equivalents with respect to catalyzer) add Teflon In the crucible.Airtight autoclave, and with argon purge 3 times.Add 15ml tetrahydrofuran (THF), 5ml vinylbenzene and 60mg triethylamine (is 4 equivalents with respect to catalyzer) subsequently.Form carbon monoxide pressure (15 crust) and hydrogen pressure (15 crust) then.Under magnetic agitation, autoclave is heated to 60 ℃.,, and in 1 hour, reduce pressure after 4 hours in reaction under this temperature autoclave cooling fast in acetone/liquid nitrogen mixture.Sample by gas-chromatography (VPC) analyze reaction mixture.
Obtain following result:
-cinnamic transformation efficiency: 95%
The selectivity of-aldehydes: 97%
The ratio of-branched chain aldehyde/linear chain aldehyde: 95/5
The processional frequency of-catalyzer: 75h-1 (, getting identical VPC response factor) for all products by mean value calculation with respect to the reaction times.Embodiment 18 is by the styrene catalyzed hydrocarbonylation of Rh (I) compound (I k)
Repeat embodiment 17, use the 40mg title complex (I k) of preparation among the embodiment 16, do not use triphenyl phosphine.
,, and in 1 hour, reduce pressure after 3 hours 80 ℃ of reactions autoclave cooling fast in acetone/liquid nitrogen mixture.Sample by gas-chromatography (VPC) analyze reaction mixture.
Obtain following result:
-cinnamic transformation efficiency: 96%
The selectivity of-aldehydes: 100%
The ratio of-branched chain aldehyde/linear chain aldehyde: 25/75
The processional frequency of-catalyzer: 79h -1(, getting identical VPC response factor) for all products by mean value calculation with respect to the reaction times.

Claims (11)

1, the organometallic complex that comprises heterocycle carbine is characterized in that they are corresponding to logical formula I:
[(Z +X -) mML n] Y (I) wherein:
-Z +Represent its at least a portion annular atoms by alkyl replace 1,2,4-triazole-5-subunit ion,
-L represents ligand, and it can be ion or neutral,
-M represents to be selected from the metal of 1b in the periodic table of elements, 2b, 3b, 4b, 5b, 6b, 7b and 8 family's transition element,
-X-represents the organic or inorganic negatively charged ion,
-m represents 1～6 integer,
-n represents 0～5 integer,
-m and n sum are equal to or less than 6,
-Y represents to make metal complexes to be electroneutral negatively charged ion or positively charged ion.
2, the organometallic complex of claim 1 is characterized in that 1,2,4-triazole-5-subunit ion Z +Corresponding to logical formula II:
Figure A9980766500021
R wherein 1, R 2, R 3And R 4Can represent identical or differently:
-straight or branched alkyl or cycloalkyl,
-aryl,
-comprise one or more substituent alkyl, described substituting group for example be aryl, alkoxyl group, halogen atom or hydrophilic radical as:
-COOM 1,-SO 3M 1Or-PO 3M 1, M 1Expression is selected from the inorganic of proton or organic cation residue, be derived from the positively charged ion of basic metal or alkaline-earth metal or wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～4 carbon atom 4,
-N (R) 3Y a, symbol R can represent hydrogen atom identical or differently or have the alkyl of 1～12 carbon atom, Y in the formula aRepresent inorganic or organic anion,
-OH，
-aryl or aralkyl or on ring, comprise one or more substituent cycloalkyl, described substituting group for example be alkyl, alkoxyl group, halogen atom or hydrophilic radical as:
-COOM 1,-SO 3M 1Or-PO 3M 1, M 1Expression is selected from the inorganic of proton or organic cation residue, be derived from the positively charged ion of basic metal or alkaline-earth metal or wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～12 carbon atom 4,
-N (R) 3Y a, symbol R can represent hydrogen atom identical or differently or have the alkyl of 1～12 carbon atom, Y in the formula aRepresent inorganic or organic anion,
-OH, R 3Also represent hydrogen atom, R 1And/or R 4Also can represent separately by alkylidene group or arylidene and 1,2, the organic ligand residue of 4-triazole-5-subunit ionic nitrogen atom bonding, this ligand residue might be phosphorous acid ester residue, phosphinate residue, phosphinate residue, phosphine residue or aliphatic series, alicyclic, aromatics or heterocycle tertiary amine residue and as with the ligand L of metal M.
3, claim 1 or 2 organometallic complex is characterized in that R 1And/or R 4Expression is by alkylidene group or phenylene and 1,2, the organic ligand residue of 4-triazole-5-subunit ionic nitrogen atom bonding, described ligand residue is derived from phenyl-phosphite that replaced by substituting group defined above or unsubstituted or alkyl ester, replaced by substituting group defined above or unsubstituted phosphonous acid phenyl ester or alkyl ester, replaced by substituting group defined above or unsubstituted phospho acid phenyl ester or alkyl ester, replaced by substituting group defined above or unsubstituted phosphniline or alkylphosphines.
4, each organometallic complex in the claim 1～3 is characterized in that the neutral ligand that L represents to be selected from the ionic ligand of halogenide or prussiate or is selected from carbon monoxide, isonitrile, phosphine, organophosphite, phosphonic acid ester or phosphinate.
5, each organometallic complex in the claim 1～4 is characterized in that M represents to be selected from the metal of nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium or mercury.
6, each organometallic complex in the claim 1～5 is characterized in that the X-negatively charged ion is a weakly coordinating anion, and mainly constitutes 1,2, the 4-triazole-anti-electron ion of 5-subunit ionic.
7, the organometallic complex of claim 6 is characterized in that weakly coordinating anion X-is selected from fluoroform sulphonate, a tetrafluoro borate, hexafluorophosphate, aluminum tetrachloride, tetrabormated aluminium, tetrafluoride aluminium, tetraiodide aluminium, four gallium chlorides, tetrabormated gallium, tetrafluoride gallium or tetraiodide gallium.
8, the preparation method of the organometallic complex of logical formula I is characterized in that making the dication heterogeneous ring compound and the compounds of metal M reaction of logical formula III in the presence of inorganic or organic bases: Wherein
-symbol R 1, R 2, R 3And R 4Regard to 1,2 of formula II on having, the implication shown in 4-triazole-5-subunit ion,
-X-represents a kind of negatively charged ion, for example for shown in the logical formula I those.
9, the preparation method of claim 8, it is characterized in that by in the solution of compound (III) or suspension, adding compounds of metal M and add inorganic if desired or organic bases reacts in liquid medium, or at room temperature or preferably under 25～150 ℃ temperature the adding order by the transformationreation thing operate.
10, in the claim 1～7 organometallic complex shown in each the formula I as the purposes of chemical reaction catalyst.
11; the purposes of claim 10; be used for the particularly hydrosilylation effect of alkene or alkynes in the presence of ruthenium complexe; the hydrosilylation effect of ketone in the presence of ruthenium or rhodium complex; Heck reaction in the presence of palladium complex; at ruthenium; rhodium; there are alkene down in platinum or palladium complex; aldehyde; acid; the hydrogenization of alkene acid amides and nitroaromatic; the hydroformylation of alkene and hydroformylation effect in the presence of rhodium complex; the hydrocyanation of alkene in the presence of nickel complex; furans is synthetic in the presence of ruthenium complexe; the metathesis of alkene in the presence of ruthenium complexe, or in the presence of nickel complex the polyreaction of acrylate.
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